EP1541219B1 - Procédé pour l'élimination de NOx et de la matière particulaire - Google Patents
Procédé pour l'élimination de NOx et de la matière particulaire Download PDFInfo
- Publication number
- EP1541219B1 EP1541219B1 EP03104591A EP03104591A EP1541219B1 EP 1541219 B1 EP1541219 B1 EP 1541219B1 EP 03104591 A EP03104591 A EP 03104591A EP 03104591 A EP03104591 A EP 03104591A EP 1541219 B1 EP1541219 B1 EP 1541219B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- nox
- catalyst
- adsorption
- oxidation
- silver
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000013618 particulate matter Substances 0.000 title claims description 6
- 239000000203 mixture Substances 0.000 claims abstract description 111
- 239000003054 catalyst Substances 0.000 claims abstract description 94
- 229910052709 silver Inorganic materials 0.000 claims abstract description 79
- 230000003647 oxidation Effects 0.000 claims abstract description 55
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 55
- 238000003795 desorption Methods 0.000 claims abstract description 44
- 239000004071 soot Substances 0.000 claims abstract description 44
- 239000004332 silver Substances 0.000 claims abstract description 41
- 230000009467 reduction Effects 0.000 claims abstract description 38
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 20
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 19
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 18
- 238000001179 sorption measurement Methods 0.000 claims description 86
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 238000012360 testing method Methods 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 15
- 229910052684 Cerium Inorganic materials 0.000 abstract description 14
- 239000003463 adsorbent Substances 0.000 abstract description 11
- 230000008929 regeneration Effects 0.000 abstract description 10
- 238000011069 regeneration method Methods 0.000 abstract description 10
- 229910052777 Praseodymium Inorganic materials 0.000 abstract description 8
- 229910052723 transition metal Inorganic materials 0.000 abstract description 7
- 150000003624 transition metals Chemical class 0.000 abstract description 7
- 229910052797 bismuth Inorganic materials 0.000 abstract description 6
- 229910052802 copper Inorganic materials 0.000 abstract description 6
- 229910052742 iron Inorganic materials 0.000 abstract description 6
- 229910052748 manganese Inorganic materials 0.000 abstract description 6
- 229910052759 nickel Inorganic materials 0.000 abstract description 6
- 238000009472 formulation Methods 0.000 abstract description 5
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 165
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 60
- 229910052593 corundum Inorganic materials 0.000 description 54
- 229910001845 yogo sapphire Inorganic materials 0.000 description 54
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 48
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 38
- 238000006722 reduction reaction Methods 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 35
- 229910002092 carbon dioxide Inorganic materials 0.000 description 32
- 229910002701 Ag-Co Inorganic materials 0.000 description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 19
- 239000007789 gas Substances 0.000 description 17
- 238000011068 loading method Methods 0.000 description 16
- 238000002336 sorption--desorption measurement Methods 0.000 description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 12
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- 229910052878 cordierite Inorganic materials 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 229910017944 Ag—Cu Inorganic materials 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 239000003426 co-catalyst Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 229910001923 silver oxide Inorganic materials 0.000 description 6
- 239000000446 fuel Substances 0.000 description 5
- 229910001961 silver nitrate Inorganic materials 0.000 description 5
- 238000011144 upstream manufacturing Methods 0.000 description 5
- 229910052772 Samarium Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
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- 239000000377 silicon dioxide Substances 0.000 description 4
- 241000894007 species Species 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910017937 Ag-Ni Inorganic materials 0.000 description 3
- 229910017984 Ag—Ni Inorganic materials 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- WSWCOQWTEOXDQX-MQQKCMAXSA-M (E,E)-sorbate Chemical compound C\C=C\C=C\C([O-])=O WSWCOQWTEOXDQX-MQQKCMAXSA-M 0.000 description 2
- 229910017980 Ag—Sn Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- KKKDGYXNGYJJRX-UHFFFAOYSA-M silver nitrite Chemical compound [Ag+].[O-]N=O KKKDGYXNGYJJRX-UHFFFAOYSA-M 0.000 description 2
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 description 2
- 229940075554 sorbate Drugs 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 229910008334 ZrO(NO3)2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- -1 boria Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011217 control strategy Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
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- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000012812 general test Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical class [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
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- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/104—Silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
- B01D2255/2065—Cerium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20715—Zirconium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20746—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20761—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/209—Other metals
- B01D2255/2092—Aluminium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Definitions
- EP-1 356 864 describes a method for oxidising NO to NOx, followed by soot oxidation.
- NOx reduction under lean conditions is very challenging problem for lean-burn gasoline and diesel engines due to the lack or shortage of gaseous reducing agents, e.g. CO and hydrocarbons for selective NOx conversion to occur.
- gaseous reducing agents e.g. CO and hydrocarbons for selective NOx conversion to occur.
- Two technologies are in development to meet this problem, namely SCR (selective catalytic reduction) using additional reductant like urea (ammonia) or hydrocarbons and NOx trap (sorbate) approach.
- the SCR method allows to get a good NOx conversion using ammonia or urea, but it is complex and expensive, requires refilling of reductant, precise dosing and temperature control to avoid ammonia slip, and the reaction is accompanied by a huge amount of side products.
- the SCR with hydrocarbons, especially fuel, is more attractive, but has a lower conversion and lower selectivity towards nitrogen; N2O is a basic product at low temperatures.
- a catalyst with an additional Ag-Cu composition is described for use in such a method for reduction of NOx in a gas stream containing some reductant.
- NOx sorbate or "trap" catalysts have achieved 80-90% reduction of NOx from lean exhaust streams using 1-2 minutes of NOx adsorption under lean conditions and NOx release and reduction under short periods of rich transient conditions for 1-10 seconds.
- this method has a problem of deactivation due to the sulfur poisoning and requires the desulfation at high temperatures of 600-650°C under reducing conditions, that leads to high fuel penalty and thermal deactivation of the catalyst, so it is not possible to keep the initial high effectivity. It is very problematic to create a sulfur-tolerant NOx trap, because metal sulfates are thermodynamically more stable than nitrates. Those formulations are also very expensive due to the high Pt and typically Rh loading and require temperatures above 250°C for good NOx conversion.
- the combination of a NOx storage catalyst and diesel particulate filter for simultaneous removal of nitrogen oxides and soot is e.g. known from DE 199 45 260 A1 .
- the NOx removal without reductant is considered as impossible except as direct NO decomposition at high temperatures of typically 600-1000°C. Such temperatures are not realistic and require unrealistic fuel consumption for automotive applications.
- the invention employs to a catalyst and adsorption composition for low-temperature NOx reduction without gaseous reductant, comprising silver (Ag) or an oxide thereof and at least one second metal oxide component.
- composition surprisingly is able to remove NOx from exhaust gases at low temperatures and without the need for the addition of a gaseous reductant.
- Preferred embodiments of the composition, devices containing it, and methods using it will be described in the following.
- the silver loading of that composition is from about 1 wt.% to about 40 wt.%, and/or the molar ratio of silver to the second metal oxide component is from 5/1 to 1/2.
- the second metal oxide component of the composition is an oxide of a transition metal, especially of Co, Ni, Cu, Mn, Fe or Zn, or an oxide of Ce, Pr or Bi.
- composition comprises the combinations Ag-Ce or Ag-Co-Ce.
- the invention involves an aftertreatment device for exhaust gases, especially exhaust gases of diesel engines or lean-burn gasoline combustion engines.
- the aftertreatment device is characterized in that it comprises a composition of the kind mentioned above, i.e. comprising Ag or an oxide thereof and at least one second metal oxide component.
- composition of the aftertreatment device is deposited on a support, which may especially be alumina and/or mixed zirconia-alumina.
- composition of the aftertreatment device is applied to a substrate, which may especially be a monolithic substrate made from cordierite or SiC or to a diesel particulate filter.
- the aftertreatment device is integrally or separately combined with other aftertreatment devices, preferably a diesel oxidation catalyst (DOC), an oxidation catalyst for lean-burn gasoline, an NOx trap, a diesel particulate filter (DPF) and/or a three-way catalyst (TWC) for gasoline aftertreatment.
- DOC diesel oxidation catalyst
- DPF diesel particulate filter
- TWC three-way catalyst
- the aftertreatment device comprises a separate device (“NOx accumulator”) that contains said Ag composition, this NOx accumulator being combined with a diesel oxidation catalyst, a NOx trap and/or a diesel particulate filter located upstream and/or downstream of the NOx accumulator.
- NOx accumulator a separate device that contains said Ag composition, this NOx accumulator being combined with a diesel oxidation catalyst, a NOx trap and/or a diesel particulate filter located upstream and/or downstream of the NOx accumulator.
- the invention is directed to a method for the low-temperature NOx reduction without gaseous reductant, the method comprising NO oxidation to NO2 with the help of a composition described above, i.e. comprising Ag or an oxide thereof and at least one second metal oxide component.
- the method is carried out at a temperature of about 250°C to about 350°C.
- the invention involves a method for the low-temperature NOx reduction without gaseous reductant, this method comprising the selective conversion of NO2 with the help of a composition described above, i.e. comprising Ag or an oxide thereof and at least one second metal oxide component.
- this method is combined with the method described above, i.e. with NO oxidation to N02 with the help of said composition.
- the method is carried out at a temperature of about 20°C to about 200°C, most preferably of about 50°C to about 150°C.
- a temperature of about 20°C to about 200°C most preferably of about 50°C to about 150°C.
- two effects of the composition namely NO oxidation to NO2 on the one hand and conversion of NO2 on the other, may be carried out with the same catalytic composition but at different temperature ranges.
- the converted N02 is preferably produced by said NO oxidation.
- composition is regenerated in air and/or in diesel exhaust at about 450°C to about 600°C.
- adsorption capacity of the composition can be used repeatedly.
- the particulate matter may especially be soot coming from a diesel engine.
- soot oxidation is achieved in this case using NO2 release from said composition during desorption of adsorbed NOx as NO2, the desorption being preferably carried out at about 250°C to about 400°C.
- NOx is adsorbed using said composition at low temperatures, preferably at about 20°C to about 200°C, and soot oxidation takes place on the same composition at about 250°C to about 400°C.
- the invention involves a method for the removal of NO and NO2 from exhaust gas, characterized in that a composition described above, i.e. comprising Ag or an oxide thereof and at least one second metal oxide component, is used for NO and NO2 adsorption at low temperatures, preferably at about 20°C to about 350°C.
- a composition described above i.e. comprising Ag or an oxide thereof and at least one second metal oxide component
- NO2 is released from said composition and consumed by an internal combustion engine, the release preferably taking place at about 250°C to about 450°C.
- the invention involves the use of a composition described above, i.e. comprising Ag or an oxide thereof and at least one second metal oxide component, for low-temperature NOx reduction without gaseous reductant. This use may especially take place according to one of the methods described above.
- the invention relates to the new method of low temperature NOx reduction without gaseous reductant under absolutely lean conditions using the combination of silver with some transition metals (Co, Ni, Cu, Mn, Fe) or metal oxides of Ce, Pr or Bi as a catalyst-adsorbent.
- First step is NO oxidation to NO2 using this catalyst at 220-350°C.
- NO2 thus produced can be converted on the same catalyst from room temperature up to 200°C.
- These systems are also good adsorbents for NO and NO2 and release basically N02 during desorption. This NO2 released can be used for simultaneous soot removal.
- Engine testing of Ag-Ce and Ag-Ce-Co formulations deposited on diesel particulate filter revealed the good activity in soot oxidation and filter regeneration of such a system at 250-350°C using NOx emitted from engine.
- cordierite preliminary coated with gamma-alumina was used for preparation of Ag and combined Ag- second metal oxide core samples.
- Core samples were cut from a cordierite monolith using diamond drills.
- Silver nitrate mixed with citric acid (1/1 molar ratio) in a distilled water solution was used for Ag only impregnation, the mixture of silver nitrate with second metal oxide, e.g. cobalt nitrate, iron nitrate, cerium nitrate etc. and citric acid (1/1 molar ration of citric acid to the total amount of Ag plus second nitrate) were applied to cordierite core samples for the preparation of mixed Ag-metal oxide compositions. All samples were dried overnight at 57°C in drying box with the following calcinations at 600°C in air for 3 hours.
- silica sol, zirconia sol or tin oxide sol (Alfa) were used to coat cordierite with the following drying and calcinations at 600°C for 3 hours.
- Mixed alumina-zirconia coated cordierite was prepared by impregnation of alumina-coated cordierite with solution of zirconium acetate in diluted acetic acid with the following drying and final calcinations at 600°C for 3 h.
- the full-size diesel particulate filters were prepared by the following way:
- the core catalysts of 2,54 cm diameter ⁇ 7,62 cm length (1" ⁇ 3") were tested in a laboratory-scale flow reactor with of corresponding size.
- An electric furnace was used to heat the reactor, the furnace being designed to carry out the linear increase of temperature for a temperature programmed desorption (TPD) study.
- the temperature was monitored by a thermocouple placed in the center of the catalyst. The change of thermocouple location from inlet to outlet of core sample revealed very small temperature difference.
- a conventional flow setup was used for gas mixture preparation. All gases were of ultra high purity. The flow rates were controlled using mass flow controllers (MKS, Kunststoff, Germany). To prevent water condensation, all connections were installed in a thermobox maintaining the constant temperature of 100°C. Reactor effluents were analyzed with a HP 6890A gas chromatograph, using Porapak Q and NaX packed columns. For instant NO and NO2 analysis, the Eco-Physics NOx analyzer was utilized.
- the testing procedure was the same as for NO2 adsorption, see above, but adsorption was carried out in the reaction mixture of 550-600 ppm NO2, 9.5% O2, 5% CO2 a, 5% H2O, nitrogen as a balance, and TPD was carried out in the same mixture, but without NO2.
- the additional filters for water have been installed upstream of NOx analyzer line. Water was supplied through humidifier, and carbon dioxide was supplied using additional gas line.
- the test structure was the same as for NO2 adsorption-desorption cycles, but the reaction mixture for adsorption was as the following: 750 ppm NO, 10% O2, nitrogen as a balance.
- the reaction mixture for desorption was the same as for NO2 study, namely 10% O2 in nitrogen.
- the adsorption study was performed at additional temperatures within 50-350°C range.
- the NO concentration reached the initial level in contrast to NO2 adsorption.
- test features were the same as for NO2 adsorption-desorption, see 1a-1d, but the samples were exposed to the reaction mixture of 550 ppm NO2, 750 ppm NO, 9.5% O2, N2 as a balance during adsorption isotherm study, while desorption was studied in 10% O2-N2 mixture.
- test structure and features were the same as for NO2 adsorption-desorption, see 1a-1d, but the samples were exposed to the reaction mixture of 550 ppm NO2, 9.5% 02, 5% H2O, 5% CO2, N2 as a balance during adsorption.
- the desorption was studied using the mixture of 9.5% 02, 5% H2O, 5% CO2, N2 as a balance.
- test structure and features were the same as for section 4, but with addition of 5% H2O and 5% CO2 to the mixture for adsorption and desorption.
- the powder samples were tested using Cahn 2000 TG (thermo gravimetric analyzer) operating in a flow mode.
- a powdered or "as prepared" catalyst sample was mixed (loose contact) by spatula with fresh diesel soot in ratio of 5/4, typically 25 mg of catalyst to 20 mg of Diesel soot placed into the TGA reactor, and exposed at different temperatures (200-600°C) to gas flow (50 cc/min) containing: 10% O2-N2; 1000 ppm NO2-N2; or 10% O2 - 1000 ppm NO2-N2.
- gas flow 50 cc/min
- Helium UHP 100 sccm was used to purge the microbalance chamber.
- sample filters were tested on an engine dynamometer with a Ford Lynx 1.8L engine equipped with a commercial DOC (diesel oxidation catalyst) in a close-coupled position. Stage III and Stage IV fuels were used for comparative tests.
- the commercial Pt-coated DPFs with Pt loading of 100g per cubic feet was tested as reference DPF.
- Test protocol included high-temperature cleaning of the DPF at 3000 rpm/160 Nm (425 +/-25°C; 230 kg/hr); soot loading at 2500 rpm/50 Nm (225°C, 160 +/- 20 kg/hr, soot rate loading ca. 4 g/hr, EGR on); regeneration at 2000 rpm and load increased by steps from 30 to 150 Nm to get pre-DPF temperature increase with 25°C steps from 200 to 450°C holding 15 min at each temperature; all stages described above were performed with switched off EGR.
- the silver oxide is very unstable, less stable than any other oxide including platinum-group metal oxides.
- the decomposition of silver oxide Ag2O to silver is starting at 160°C and oxygen pressure reaches 1 atm (bar) already at 185-190°C (G. Remi, Inorganic Chemistry, IIL, Moscow 1963, v.2 p.427).
- the NO2 concentration was within the range of 550-600 ppm, higher than typical for diesel engine conditions for modem diesel engines. Under such conditions the catalyst can effectively work for many hours however due to the slow silver oxidation, one can see on Figure 1 , that NOx concentration was still lower (500 ppm) than inlet NO2 concentration 550 ppm after more than 14 hours of reaction, the total amount of NO2 passed was 68.64 mmol, the difference between inlet NO2 and outlet NOx was 26.54 mmol, but only 6.31 mmol of NOx was desorbed during desorption.
- the catalyst is active even at room temperature, the conversion was found at 20°C, with NO2 selective conversion of 23% for 9 hours, as shown in Figure 2 .
- the decrease of activity is accompanied with lower conversion of NO2 to NO, as shown on Fig. 1 and Fig. 2 , it leads to increase in NO2 concentration and decrease of NO concentration and indicates the decrease of reduction properties of catalyst with time on stream.
- the NO2 adsorption was also lower at higher temperatures (250°C and 350°C), as shown in Table 3. Complete adsorption and desorption data are presented in this Table 3. All adsorbed NOx species can be completely removed at T ⁇ 450°C.
- NO2 conversion can be done without any gaseous reductant with NO2 adsorption and conversion at room temperature - 200°C and following desorption at higher temperatures.
- NO2 can be converted and adsorbed at low-speed driving and than the catalyst can be regenerated in passive mode during high-speed driving or regeneration can be done by different methods of raising temperature of diesel exhaust (throttling, post-injection etc).
- Some selected catalysts in NO2-H2O-CO2 mixtures imitating diesel exhaust were tested, see Figures 6-9 and Tables 4.1-4.4 and 5.1-5.2. Water and carbon dioxide are not strongly competing with NOx for the adsorption centers in contrast to NOx trap materials.
- adsorption capacity in the presence and in the absence of H2O and CO2 was comparable, see Tables 4.1-4-4.
- the Ag-Pr catalyst was still active in the complete mixture imitating diesel exhaust, containing NO, NO2, CO2 and water, as one can see on Fig. 8 .
- the outlet NOx concentration was only 1030 ppm after 3 hours on-stream, while inlet NOx concentration was 1280 ppm (730 ppm NO and 550 ppm NO2) at 50°C and GHSV of 5000 hr -1 on Ag-Pr catalyst, Ag-Co catalyst showed similar activity at 50°C.
- the big concentrations of NO in the presence of water and carbon dioxide suppress the activity of Ag-Co catalyst at 150°C, however, Table 4.2.
- Ag-Pr catalyst even had better performance for NO2 conversion in the presence of NO, CO2 and H2O than when only NO2 was passed through catalyst at 50°C, and had better performance at 150°C for complete mixture, Tables 5.1 and 5.2.
- NO2 was released from this Ag-Pr catalyst during desorption after NOx adsorption in a complete mixture imitating diesel exhaust (NO-NO2-CO2-H2O-O2), as shown on Figure 9 .
- the diesel exhaust contains basically NO and only a small fraction of NO2.
- the catalysts tested are not active in selective NO conversion, the difference between inlet and total outlet plus desorbed amount did not exceed 5% during NO adsorption. So for the effective conversion of NOx emissions from the diesel engine the oxidation of NO to NO2 should be preliminary done upstream of such a catalyst.
- the commercial diesel oxidation catalyst, designed for NO oxidation may be installed upstream of the catalyst presented in this invention. But the interesting feature of the catalyst of the present invention was found, namely that it becomes very active itself in NO oxidation to NO2 when temperature exceeds 200°C.
- the catalyst has no NO oxidation activity and only can adsorb NO at 150°C.
- NO oxidation occurs at 220°C, and the catalyst can practically completely convert NO to NO2 at 250°C up to the thermodynamic equilibrium level. The conversion was lower at 350°C due to the thermodynamic limitations.
- Those catalysts of this invention are also good adsorbents for NO, though adsorption capacity is lower in comparison with NO2.
- the NO adsorption capacity was 1.5-1.7 mmol/core sample at 50-200°C for Ag-Co (1.2/1), 20wt%Ag catalyst, but increased to 1.9 mmol at 220°C and 3.9 mmol at 250°C due to the NO oxidation, so the mixture of NO and NO2 was really adsorbed under these temperatures, Tables 4. At 350°C the adsorption capacity decreased again due to the intensive desorption of both NOx species.
- silver-based catalytic systems change their properties from reductive to oxidative near 200°C, being active up to 200°C in NO2 reduction and active in NO oxidation above 200°C.
- Those features allow to carry out the two-stage process of NO oxidation to NO2 and following NO2 removal using the same catalyst, e.g. Ag-Co, but maintaining it at different temperatures.
- the first part of catalyst can effectively oxidize NO to NO2 at 250-300°C, while the second part downstream can convert NO2 at temperatures from room to 200°C.
- the good adsorption properties also allow the other possible way, because these catalysts, especially with low silver loading, release basically NO2 after NO adsorption, so the systems can oxidize adsorbed NO to NO2 with increasing temperature and release it as NO2.
- NO2 As shown on Fig. 13 , after NO adsorption at 150°C the amount NO2 released was near 7 times higher than amount of NO released during desorption. The same picture was observed for other adsorption temperatures, except 50°C, where some amount of NO was released at 100-130°C.
- compositions can be deposited on a separate device (or devices), called “NOx accumulator", e.g. deposited on a monolithic substrate made of cordierite, SiC or other material.
- NOx accumulator e.g. deposited on a monolithic substrate made of cordierite, SiC or other material.
- This device can provide some passive NOx reduction, but its effectivity can be improved using an active control strategy to maintain the temperature necessary for good NOx adsorption and reduction and catalyst regeneration.
- those compositions can be applied to diesel oxidation catalyst, NOx trap, diesel particulate filter or other aftertreatment devices to improve their performance.
- the catalysts-adsorbents can be used for NOx accumulation with the following NO2 return to engine for consumption using for example an EGR valve installed before DPF.
- the catalysts-adsorbents of the present invention can also be combined with an NOx trap or conventional TWC (three-way catalyst) to improve their performance.
- the property of the catalysts-adsorbents of this invention to release basically NO2 after NOx adsorption can be used for simultaneous removal of NOx and particular matter, as it will be described below.
- the presence of silver is of basic importance, because only silver can reduce NO2 due to its metallic property, the testing with the second metal oxide component did not reveal any NO2 reduction.
- the second component is also very important, because pure silver can effectively reduce NO2 only at a high concentration of silver (35 wt.%) that is not practical.
- the second component is able not only to reduce the silver loading, but also improve the performance in comparison with any only silver composition, especially at 150°C.
- Ag-Co catalyst with 5 wt.% Ag loading gives practically the same activity as catalyst with 35 wt.% only silver loading, while Ag-Co with 20 wt.% Ag has better performance in comparison with any pure silver catalyst, as one can see in Tables 1 and 2.
- the ratio of Ag/second component can be varied from 5/1 to 1/2, the high loading of second component usually decreases the activity.
- the silver loading can be varied from 1 to 40wt.%, preferably 5-20wt.%.
- the lower silver loading usually led to decreased adsorption capacity, but often kept the same level of NO2 conversion.
- the time of effective catalyst work decreased however due to the lower silver concentration.
- those compositions have the valuable property to release practically only NO2 during desorption, as one can see on Figure 14 . This property is very valuable for soot oxidation, because only NO2 is able to oxidize soot at low temperatures.
- compositions presented in this application are active in soot oxidation in the presence of NO2 and can be used for simultaneous removal of NOx and particulate matter (soot) from diesel engine.
- compositions can be deposited on a separate device (NOx accumulator) to collect NOx at low temperatures and to release NO2 at temperatures of 250-400°C for oxidation of soot collected on particulate filter, but may also be deposited directly on diesel particulate filter.
- NOx accumulator NOx accumulator
- Full-size particulate filters were prepared to evaluate this possibility with Ag-Ce and Ag-Co-Ce compositions and soot oxidation was studied under real conditions using a Ford engine.
- compositions presented in this application can be in service also for simultaneous removal of soot and NOx reduction, especially Ag-Ce and Ag-Co or a mixture thereof.
- NOx accumulator installed upstream of a diesel particulate filter (DPF).
- DPF diesel particulate filter
- NOx accumulator will collect NOx emitted from engine at low temperatures, while DPF will simultaneously collect soot. Then this accumulator will release basically NO2 to the filter downstream for NO2 consumption with soot deposited on filter at 250-350°C with filter regeneration due to the soot oxidation by NO2.
- the formulations of the present invention can be deposited directly on a filter with the same function.
- catalysts-adsorbents were found and further a method for low-temperature NOx reduction without any gaseous reduction agent for diesel and lean-bum gasoline aftertreatment with NO oxidation to NO2 at 250-350°C and NO2 selective reduction on the same catalyst from room temperature to 200°C. Raising temperature to 450°C in the presence of oxygen can regenerate the catalysts.
- the catalysts-adsorbents of the present invention are combinations of silver (1-40 wt.%, preferably 5-20%) with transition metals of Co, Ni, Cu, Mn, Fe, Zn or oxides of Ce, Pr and Bi with Ag/second metal oxide molar ratio from 5/1 to 1/2.
- compositions revealed good adsorption properties for NO and NO2 and basically release NO2 during desorption.
- the same compositions, especially Ag-Ce and Ag-Co-Ce, are active in soot oxidation at 250-350°C in the presence of NOx and can be used for simultaneous removal of NOx and particulate matter.
- the compositions of this invention can be in service as separate device (NOx accumulator) or may be deposited on other aftertreatment devices, especially on diesel particulate filters.
- the ratio e.g. (1/1) in parentheses is molar ratio of silver to second component.
- Table 4.1 NOx - adsorption / desorption on catalyst Ag-Co(1.2/1), 20 wt.% Ag at Tads 50°C Mixture 9,5%O 2 +N 2 + CNOx in / (ppm) t ads / h AC in / mmol ACdif / mmol AD / mmol ⁇ AC / mmol CNOx out / (ppm) ⁇ C (ppm) NO 785 1,2 8,15 1,56 1,50 0.06 763 25 NO 2 , 6 hours 570 6,0 29,50 16,72 6,77 9,55 310 260 NO2, 3 hours 585 3,0 15,04 9,66 5,66 4,00 305 280 NO+NO 2 780 + 535 3,0 33,81 5,47 3,36 (+0,2) 1,91 1198 117 NO2+5%CO 2 +5%H 2 O 570 3,14 15,36 8,22 5,61 (+0,26) 2,35 570
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Claims (9)
- Méthode pour la réduction des NOx à basse température, ladite méthode comprenant :une première étape d'oxydation de NO en NO2 à l'aide d'une composition catalytique d'adsorption comprenant de l'argent et au moins un deuxième composant d'oxyde métallique ; etune deuxième étape de conversion sélective du NO2 à une température de l'ordre de 20°C à 200°C à l'aide de ladite composition catalytique d'adsorption ;chacune desdites première et deuxième étapes étant effectuée sans agent réducteur gazeux.
- Méthode selon la revendication 1, caractérisée en ce que ladite conversion sélective est effectuée à une température de l'ordre de 50°C à 150°C.
- Méthode selon la revendication 1 ou 2, caractérisée en ce que ladite composition catalytique d'adsorption comprend de l'argent en tant qu'oxyde.
- Méthode selon l'une quelconque des revendications 1 à 3, caractérisée en ce que ladite première étape est effectuée à une température entre environ 250°C et environ 350°C.
- Méthode selon l'une quelconque des revendications 1 à 4, caractérisée en ce que le NO2 converti a été produit par ladite oxydation de NO.
- Méthode selon l'une quelconque des revendications 1 à 5, caractérisée en ce que ladite composition est régénérée dans de l'air et/ou dans un échappement diesel entre environ 450°C et environ 600°C.
- Méthode selon l'une quelconque des revendications 1 à 6, caractérisée en ce que le NOx et des matières particulaires, en particulier de la suie, sont éliminés simultanément.
- Méthode selon la revendication 7, caractérisée par l'oxydation de la suie en utilisant du NO2 libéré par ladite composition au cours de la désorption du NOx adsorbé sous forme de NO2, la désorption étant de préférence effectuée entre environ 250°C et environ 400°C.
- Méthode selon la revendication 7 ou 8, caractérisée en ce que le NOx est adsorbé en utilisant ladite composition à basses températures, de préférence entre environ 20°C et environ 200°C, et en ce que l'oxydation de la suie a lieu sur la même composition entre environ 250°C et environ 400°C.
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AT03104591T ATE424919T1 (de) | 2003-12-08 | 2003-12-08 | Verfahren zur entfernung von nox und teilchenförmigem material |
DE60326602T DE60326602D1 (de) | 2003-12-08 | 2003-12-08 | Verfahren zur Entfernung von NOx und teilchenförmigem Material |
EP03104591A EP1541219B1 (fr) | 2003-12-08 | 2003-12-08 | Procédé pour l'élimination de NOx et de la matière particulaire |
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Cited By (1)
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US8783017B2 (en) | 2010-03-11 | 2014-07-22 | Cummins Inc. | System, method, and apparatus to engage alternate reductant in a NOx reduction system |
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CN100409940C (zh) * | 2006-07-17 | 2008-08-13 | 大连理工大学 | 一种同时脱除汽车尾气中氮氧化物和一氧化碳的催化剂 |
EP1990082B1 (fr) | 2007-05-11 | 2011-08-17 | Ford Global Technologies, LLC | Catalyseur sans métal noble par l'oxidation de la suie |
US8097554B2 (en) | 2009-02-09 | 2012-01-17 | Airflow Catalyst Systems, Inc. | Apparatus for removing soot from diesel engine exhaust streams at temperatures at or below 150° C. |
JP5882916B2 (ja) | 2010-02-23 | 2016-03-09 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | 改良された触媒化された煤フィルター |
US8745971B2 (en) | 2010-03-11 | 2014-06-10 | Cummins Inc. | System, method, and apparatus for controlling an aftertreatment system having a particulate filter and a rich NOx conversion device |
US9308497B2 (en) | 2010-10-04 | 2016-04-12 | Basf Corporation | Hydrocarbon selective catalytic reduction catalyst for NOx emissions control |
US8524182B2 (en) | 2011-05-13 | 2013-09-03 | Basf Se | Catalyzed soot filter with layered design |
KR101980392B1 (ko) | 2011-05-13 | 2019-05-20 | 바스프 에스이 | 층상 구조의 촉매화된 매연 필터 |
GB201111553D0 (en) | 2011-05-20 | 2011-08-24 | Johnson Matthey Plc | NOx reduction catalyst |
DE102013207921B4 (de) * | 2012-05-07 | 2021-04-22 | GM Global Technology Operations, LLC (n.d. Ges. d. Staates Delaware) | Verfahren zur Stickstoffmonoxid-Oxidation über silber-basierten Katalysatoren und katalytischer Reaktor |
DE102013207922B4 (de) * | 2012-05-07 | 2021-04-22 | GM Global Technology Operations, LLC (n.d. Ges. d. Staates Delaware) | Verfahren zur Behandlung eines Abgasstroms mit einem Silber-gestützten enggekoppelten NOx-Absorber |
US8920756B2 (en) * | 2012-05-07 | 2014-12-30 | GM Global Technology Operations LLC | Silver promoted close-coupled NOx absorber |
CN110072609A (zh) | 2016-10-18 | 2019-07-30 | 巴斯夫公司 | 用于柴油车辆的使用h2-scr的低温nox还原 |
US10392980B2 (en) | 2017-03-22 | 2019-08-27 | Ford Global Technologies, Llc | Methods and systems for a diesel oxidation catalyst |
US10598061B2 (en) | 2017-03-22 | 2020-03-24 | Ford Global Technologies, Llc | Methods and systems for a diesel oxidation catalyst |
CN113145126B (zh) * | 2021-03-11 | 2023-03-24 | 中国科学院城市环境研究所 | 一种复合催化剂及其制备方法和应用 |
CN115430431B (zh) * | 2022-08-19 | 2024-05-17 | 河南农业大学 | 一种Mn掺杂的Co基催化剂、其制备方法以及应用 |
CN115318303B (zh) * | 2022-08-25 | 2024-03-01 | 上海净舒汽车技术服务中心 | 一种低温去除柴油车碳烟颗粒的催化剂及其制备方法 |
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US5206196A (en) * | 1990-12-18 | 1993-04-27 | Tosoh Corporation | Catalyst for purifying exhaust gas |
JPH11342339A (ja) * | 1998-03-31 | 1999-12-14 | Mazda Motor Corp | 排気ガス浄化用触媒 |
EP1378289A3 (fr) * | 2002-04-18 | 2004-02-04 | Ford Global Technologies, LLC, A subsidary of Ford Motor Company | Revêtements catalytiques exempt de métal du groupe du platine dans des filtres à particules pour gaz d'échappement |
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US8783017B2 (en) | 2010-03-11 | 2014-07-22 | Cummins Inc. | System, method, and apparatus to engage alternate reductant in a NOx reduction system |
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